AU647060B2 - Method for preparing emulsion polymerized polybutadiene of increased particle size - Google Patents
Method for preparing emulsion polymerized polybutadiene of increased particle size Download PDFInfo
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- AU647060B2 AU647060B2 AU68246/90A AU6824690A AU647060B2 AU 647060 B2 AU647060 B2 AU 647060B2 AU 68246/90 A AU68246/90 A AU 68246/90A AU 6824690 A AU6824690 A AU 6824690A AU 647060 B2 AU647060 B2 AU 647060B2
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- emulsion polymerization
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- butadiene
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- 238000000034 method Methods 0.000 title claims description 36
- 239000002245 particle Substances 0.000 title description 38
- 239000005062 Polybutadiene Substances 0.000 title description 15
- 229920002857 polybutadiene Polymers 0.000 title description 15
- 239000000839 emulsion Substances 0.000 title description 4
- 229920000126 latex Polymers 0.000 claims description 49
- 239000004816 latex Substances 0.000 claims description 42
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 35
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 25
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 23
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 239000000344 soap Substances 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 3
- 150000003254 radicals Chemical class 0.000 claims description 3
- 239000012986 chain transfer agent Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 238000013019 agitation Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000005054 agglomeration Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229920003051 synthetic elastomer Polymers 0.000 description 4
- 239000005061 synthetic rubber Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 229920006174 synthetic rubber latex Polymers 0.000 description 3
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- -1 alkali metal sulfonates Chemical class 0.000 description 2
- 238000004581 coalescence Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- JZBWUTVDIDNCMW-UHFFFAOYSA-L dipotassium;oxido sulfate Chemical compound [K+].[K+].[O-]OS([O-])(=O)=O JZBWUTVDIDNCMW-UHFFFAOYSA-L 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 229940096992 potassium oleate Drugs 0.000 description 2
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- KAKVFSYQVNHFBS-UHFFFAOYSA-N (5-hydroxycyclopenten-1-yl)-phenylmethanone Chemical compound OC1CCC=C1C(=O)C1=CC=CC=C1 KAKVFSYQVNHFBS-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical compound ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241000613130 Tima Species 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-M hexadecanoate Chemical compound CCCCCCCCCCCCCCCC([O-])=O IPCSVZSSVZVIGE-UHFFFAOYSA-M 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 150000004668 long chain fatty acids Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229940105132 myristate Drugs 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C1/00—Treatment of rubber latex
- C08C1/02—Chemical or physical treatment of rubber latex before or during concentration
- C08C1/065—Increasing the size of dispersed rubber particles
- C08C1/07—Increasing the size of dispersed rubber particles characterised by the agglomerating agents used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F36/06—Butadiene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
Description
S ur Ref: 345274 647060
AUSTRALIA
Patents Act COMPLETE SPECIFICATION FORM
(ORIGINAL)
Application Number: Lodged: Complete Specification Lodged: Accepted: Published: *0 0 0*ce .00 p *0 0 .s p 0 0
S
*0 Priority: Related Art: Applicant(s): Address for Service: General Electric Company 1 River Road SCHENECTADY New York UNITED STATES OF AMERICA ARTHUR S. CAVE CO.
"atent Trade Mark Attorneys Level 10, 10 Barrack Street SYDNEY NSW 2000 Complete specification for the invention entitled "~iethod for preparing emulsion polymerized polybutadiene of increased particle size".
The following statement is a full description of this invention, including the best method of performing it known to me:- 1 5020 007-048 (8CP12008) l a- METHOD FOR PREPARING EMULSION POLYMERIZED POLYBUTADIENE OF INCREASED PARTICLE SIZE FIELD OF THE INVENTION i The present invention relates to methods for preparing polybutadiene having an increased average particle size. More particularly, the present invention 5 relates to emulsion polymerization methods for preparing polybutadiene having an increased average particle size.
BACKGROUND OF THE INVENTION 0e0 0The viscosity of synthetic rubber latex a comprising polybutadiene at a given temperature and solids 10 content is largely determined by the average particle size S" and the distributi.on of particle size of the polybutadiene. Generally, a large average particle size is desirable and results in a lower viscosity latex at a given solids content and temperature. Various techniques i 5 have been employed to inc-ease the particle size of a rubber latex during emulsion polymerization. However, difficulties have been encountered with each of these techniques.
For example, Chittenden et al, Industrial and Engineering Chemistry, 40, 337 (1948), and Borders et al, Industrial and Engineering Chemistry, 40, 1473 (1948), disclose the use of high organic monomer to water ratios or low soap concentrations to promote agglomeration during emulsion polymerization reactions of butadiene. However, this technique results in one or more periods of instability during which coagulation may occur.
Additionally, heat removal may be difficult because of high viscosity conditions and, if the reaction proceeds in an uncontrolled manner during the critical coalescent 10 stage, it is often difficult to reproduce desirable reaction results.
It is also known to add colloidally active compounds to a rubber latex in order to increase the particle size. For example, the Howland et al U.S. Patent .*65 No. 3,056,758 teaches the addition of polyvinylmethyl ether to a synthetic rubber latex in order to increase the particle size while the Schluter U.S. Patent No. 3,330,795 discloses the addition of a polyalkylene oxide to a synthetic rubber dispersion to cause agglomeration.
Attempts have also been made to add colloidally active S compounds to the emulsion polymerization recipe. For example, Belgian Patent No. 817,505 discloses the addition of a polyalkylene glycol agglomerating agent while Araki, Polymer Journal, Vol. 19, No. 7, 863 (1987) discloses the addition of sodium alganate and magnesium sulfate to the emulsion reaction. However, these methods are disadvantageous in that oftentimes low monomer conversion rates are realized resulting in reactions that may require as long as 70 hours to reach completion.
The Gauslaa U.S. Patent No. 3,318,831 discloses a method for the production of large particle latices in short reaction times using high-sheer techniques during 3 polymerization. However, this method is disadvantageous in that it requires special reactors capable of high agitation rates.
Thus, a need still exists for improved methods for providing synthetic rubber latices having increased particle size.
SUMMARY OF THE INVENTION Accordingly, it is an object of the present S, 10 invention to provide an improved method for preparing synthetic rubber latices of increased particle size. It is a further object of the present invention to provide methods for preparing polybutadiene of increased particle size. An additional object of the invention is to provide 15 emulsion polymerization methods for preparing polybutadiene of increased particle size.
These and additional objects are provided by the present invention which relates to methods for emulsion polymerization of butadiene. According to the present 20 invention, an acryli: latex is added to the emulsion polymerization medium during the polymerization reaction in an amount effective to increase the average particle S size of the resulting polybutadiene latex. The present Smethods are advantageous in that they generally are 25 insensitive to temperature and agitation rates, they do ot induce a period of bulk instability during the emulsion polymerization reaction, and the reaction proceeds rapidly once the acrylic latex is introduced.
Additionally, the particles of the resulting polybutadiene latex may also exhibit a desirable spherical shape.
These and additional objects and advantages will 4 be more fully understood in view of the following detailed description.
DETAILED DESCRIPTION In the ensuing description, the invention will be sequentially described with reference to preferred performance features and illustrative numerical Examples. It will therefore be understood that such ensuing description should not be limitatively construed.
In preparing the synthetic rubber latices of the present invention, one or more butadienes -1,3 may be employed including, for example, butadiene 2-methylbutadiene-1,3 (isoprene), 2,3-dimethyl-butadiene-1,3 and piperylene. Additionally, a mixture of one or more of such butadienes -1,3 with one or more comonomers which are capable of forming rubbery copolymers with butadienes -1,3 may be employed.
15 Preferred comonomers include one or more monoethylenic compounds which contain a
CH
2 group where at least one of the disconnected valences is attached to an electronegative group, that is, a group which substantially increases the electrical disymmetry or polar character of the molecule. Examples of such compounds which are copolymerizable with butadiene are aryl olefines such as styrene, vinyl toluene, alpha- 20 methylstyrene, chlorostyrene, dichlorostyrene and vinyl naphthalene, with styrene being a preferred comonomer. The comonomer may be included with the butadiene in an :i amount up to about 50% by weight of the resulting monomer mixture.
As noted above, the acrylic latex is added to an emulsion polymerization medium containing butadiene, and optionally a ccnonomer, during the polymerization reaction 3B:\US01\345274\A1 in an amount effective to increase the average particle size of the resulting polybutadiene latex. Preferably, the acrylic latex is added to the emulsion polymerization medium in an amount effective to increase the average particle size of the resulting polybutadiene latex to at least about 200 nm as measured by the turbidity method.
Generally, the acrylic latex is added to the emulsion polymerization medium in an amount of at least about 0.1 parts by weight, on a dry basis, per 100 parts by weight of butadiene included in the emulsion polymerization medium. Preferably, the acrylic latex is added in an amount of from about 0.1 to about 10 parts by weight, on a dry basis, and more preferably in an amount of from about 1 to about 5 parts by weight, on a dry basis, per 100 15 parts by weight of butadiene included in the eiulsion polymerization medium.
Generally, the acrylic latex suitable for use in the *methods of the present invention may comprise any of the acrylic latices which are well known in the art. In a prferred embodiment, the acrylic latex comprises a polyalkylacrylate latex or a poly(alkylmethacrylate) latex. As demonstrated in the examples set forth below, a S particularly preferred acrylic latex which has been employed in the present methods comprises a 25 poly(alkylacrylate-co-methacrylic acid) latex such as poly(butylacrylate-co-methacrylic acid) latex.
The general methods of emulsion polymerization of butadiene are well known in the art. Typically, the emulsion polymerization medium includes a soap or surfactant, a free radical initiator and a chain transfer agent, all of which are well known in the art. Examples of suitable soaps/surfactants include fatty acid soaps and especially water soluble, long chain fatty acid soaps such as sodium or potassium laurate, myristate, palmitate, oleate and stearate. Water soluble sodium or potassium soaps of tall oil and the rosin soaps, including disproportionated rosin soaps, may also be used. If desired, a secondary surfactant may be present, examples of which include alkali metal sulfonates derived from aryl sulfonic acids such as sodium alkyl naphthalene sulfonate.
Suitable free radical initiators include organic hydroperoxides and ionizable heavy metal salts. Suitable ;chain transfer agents include the well known mercaptantype compounds.
To one of ordinary skill in the art, it would *0 appear that addition of an acrylic latex at the beginning 15 or during the emulsion polymerization reaction would provide similar results as are encountered with the addition of colloidally active agents employed in the prior art, namely particles begin to agglomerate shortly after forming, whereby the number of particles is reduced •:20 early in the reaction thereby resulting in very long S* reaction timas. However, the present inventor has discovered that in fact, synthetic rubber latex particles S of an increased size can be formed according to the present methods without requiring long reaction times.
*25 While the present invention is not intended to be limited *o by the following, it is the inventor's belief that a S* majority of the monomer is polymerized in small particles which takes advantage of the high particle number kinetics, and the reaction is then completed after the particles have been agglomerated, thereby resulting in large size particles in reduced reaction times.
Additionally, the monomer-swollen particles appear to be softer and more deformable during the agglomeration whereby complete coalescence may be obtained. Coalescence of the particles, coupled with the natural tendency toward formation of spherical particles during the completion of the polymerization, may result in the particles having a desirable spherical shape.
The present methods are advantageous in that the acrylic latex induced agglomeration is generally insensitive to temperature and agitation rate, the method 10 does not induce a period of bulk instability in the emulsion polymerization process, and the polymerization reaction occurs very rapidly once the acrylic latex is introduced. Additionally, it appears that small particles introduced after the acrylic latex is added are also agglomerated. The agglomeration of these new particles by the acrylic latex may lead to a narrower particle size distribution than is produced by other polymerization/ agglbmeration methods. The reduction of total surface area when the particles agglomerate may result in the 20 release of soap which normally leads to a new generation of small particles unless the reaction conditions prevent such.
The following examples serve to illustrate specific embodiments of the invention.
S EXAMPLE 1 A twelve-ounce citrate bottle was charged with 100 parts by weight butadiene, 3.5 parts by weight potassium oleate, 0.356 parts by weight tetrasodium pyrophosphate, 0.14 parts by weight potassium peroxysulfate, 0.2 parts by weight tert-dodecyl mercaptan and 230 parts by weight demineralized water, and then fitted with a rubber septum. The medium was heated at 49°C for seven hours to commence polymerization. The temperature was then raised to 65 0 C and 2.0 parts by weight (dry basis) of an acrylic latex agglomerating agent was addea. The acrylic latex comprised a 20/80 methacrylic acid/butyl acrylate copolymer. The resulting poiybutadiene latex had a particle size of 330 nm as measured by the turbidity method.
EXAMPLE 2 A pressure reactor was charged with 100 parts by weight butadiene, 3.5 parts by weight potassium oleate, 0.356 parts by weight tetrasodium pyrophosphate, 0.2 parts by weight tert-dodecyl mercaptan and 220 parts by weight demineralized water. The mixture was heated to 140 F with agitation. The polymerization reaction was then initiated by adding 0.14 parts by weight of potassium peroxysulfate dissolved in 10.0 parts by weight demineralized water in a shot manner. At 65% conversion to polymer, the S 20 temperature was raised to 155 F. At 80% conversion to polymer, the agitation was raised to promote rapid mixing and 3.0 parts by weight (dry basis) of the acrylic latex agglomerating agent described in Example 1 was added in a shot manner. After one minute, the agitation rate was 25 returned to normal. The reaction was continued and run to 0e 91.5% conversion in 17 hours, resulting in a latex having less than 0.2% coagulum, an average particle diameter of 290 nm as measured by the turbidity method, and the following particle-size fractions, by weight: 2.85% 100 nm, 34.5% 250 nm, and 99.02% 400 nm in diameter. The resulting polybutadiene was sufficiently stable to be grafted with styrene and acrylonitrile and was useful as an impact modifier in various thermoplastics.
EXAMPLE 3 In this example, polybutadiene was prepared in a manner similar to that employed in Eximple 2 except that in place of the 3.0 parts by weight (dry basis) of the acrylic latex agglomerating agent employed in Example 2, parts by weight (dry basis) of the acrylic latex agglomerating agent, was used in this example. The reaction ran to 91.0% conversion in 17 hours and provided a latex with an average particle diameter of 245 nm as measured by the turbidity method and containing less than 0.01% coagulum. This latex was also stable to grafting S* 15 with styrene and acrylonitrile.
The preceding examples are set forth to illustrate specific embodiments of the invention and are not 'intended to limit the scope of the methods and products of the present invention. Additional embodiments 20 and advantages within the scope of the claimed invention will be apparent to one of ordinary skill in the art.
Sb C 0
Claims (9)
1. A method for emulsion polymerization of butadiene in an emulsion polymerization medium, comprising providing an emulsion polymerization medium containing butadiene and a soap, and adding an acrylic latex to the emulsion polymerization medium during the polymerization reaction in an amount of from about 0.1 to 10 parts by weight, on a dry basis, per 100 parts by weight of butadiene included in the emulsion polymerization medium.
2. A method as defined by claim 1, wherein the acrylic latex is added to the emulsion polymerization medium in an amount from about 1 to 5 parts by weight, on a dry basis, per 100 parts by weight of butadiene included in the emulsion polymerization ,3o medium. S 15
3. A method as defined by claim 1, wherein the acrylic latex comprises a polyalkylacrylate latex.
4. A method as defined by claim 1, wherein the acrylic latex comprises a poly(alkylmethacrylate) latex.
5. A method as defined by claim 1, wherein the acrylic latex comprises a poly(alkylacrylate-co-methacrylic acid) latex.
6. A method as defined by claim 5, wherein the acrylic latex comprises poly(butylacrylate-co-methacrylic acid) latex.
7. A method as defined by claim 1, wherein the emulsion polymerization medium further comprises a free radical initiator and a chain transfer agent.
8. A method as defined by claim 1, wherein the emulsion polymerization medium further comprises a comonomer for polymerization with butadiene. B:VGS01\345274\AB 11
9. A method as detinod by claimi 8, whercin the cornonomner comprises styrine. DATED this 14th day of January, 1994. GENERAL ELECTRIC [0 COMPANY By Its Patent Attorneys DAVIES COLLISON CAVE V 13:VCSOl\34S274\A3
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US454544 | 1989-12-21 | ||
| US07/454,544 US5294659A (en) | 1989-12-21 | 1989-12-21 | Method for preparing emulsion polymerized polybutadiene of increased particle size |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU6824690A AU6824690A (en) | 1991-06-27 |
| AU647060B2 true AU647060B2 (en) | 1994-03-17 |
Family
ID=23805043
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU68246/90A Ceased AU647060B2 (en) | 1989-12-21 | 1990-12-19 | Method for preparing emulsion polymerized polybutadiene of increased particle size |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5294659A (en) |
| EP (1) | EP0433710B1 (en) |
| JP (1) | JP3162703B2 (en) |
| KR (1) | KR100201674B1 (en) |
| AU (1) | AU647060B2 (en) |
| CA (1) | CA2030615A1 (en) |
| DE (1) | DE69021179T2 (en) |
| ES (1) | ES2075870T3 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5336720A (en) * | 1991-06-05 | 1994-08-09 | Rohm And Haas Company | Impact resistant polymers |
| DE4344992A1 (en) * | 1993-12-30 | 1995-07-06 | Huels Chemische Werke Ag | Aqueous, highly concentrated synthetic rubber dispersion and its production |
| US5534594A (en) * | 1994-12-05 | 1996-07-09 | Rohm And Haas Company | Preparation of butadiene-based impact modifiers |
| US5985993A (en) * | 1996-08-01 | 1999-11-16 | Cheil Industries, Inc. | Method for preparing polybutadiene latex |
| KR100380014B1 (en) * | 1998-03-20 | 2003-08-19 | 주식회사 엘지화학 | Method for preparing rubbery polymer latex |
| US6184287B1 (en) | 1999-01-26 | 2001-02-06 | Omnova Solutions Inc. | Polymeric latexes prepared in the presence of 2-acrylamido-2-methylpropanesulfonate |
| KR100576312B1 (en) * | 1999-10-29 | 2006-05-03 | 제일모직주식회사 | Method of Preparing Synthetic Rubber Latex Having a Large Particle Size |
| US6777483B2 (en) * | 2000-10-27 | 2004-08-17 | Cheil Industries Inc. | Method of preparing diene latex having a large particle size by addition of a pretreated seed latex to an agglomerating agent |
| US20030111770A1 (en) * | 2001-12-13 | 2003-06-19 | Bridgestone Corp. | Method of improving carbon black dispersion in rubber compositions |
| CN1313506C (en) * | 2004-08-04 | 2007-05-02 | 中国石油天然气集团公司 | Polymerization method of after-agglomeration polybutadiene latex, vinyl benzene and acrylonitrile |
| DE102005022632B4 (en) | 2005-05-11 | 2022-05-25 | Ineos Styrolution Europe Gmbh | Particulate rubber, process for its production and use, and graft copolymer, thermoplastic molding material and process for its production |
| WO2009025334A1 (en) | 2007-08-21 | 2009-02-26 | Umg Abs, Ltd. | Method for producing enlarged rubber, graft copolymer, thermoplastic resin composition and molded article |
| CN103059222B (en) * | 2013-01-06 | 2017-02-15 | 杭州蓝诚新材料有限公司 | Preparation method of large-particle-size styrene-butadiene latex |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US330795A (en) * | 1885-11-17 | James macphail | ||
| FR1337809A (en) * | 1961-09-26 | 1963-09-20 | Us Rubber Co | Synthetic rubber latex of the butadiene polymer type |
| FR2235966A1 (en) * | 1973-07-06 | 1975-01-31 | Mitsubishi Rayon Co | Agglomerisation of synthetic rubber particles in latex - by addn of acrylate copolymer latex at controlled pH |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT632080A (en) * | 1959-06-24 | |||
| DE1213984B (en) * | 1963-12-05 | 1966-04-07 | Huels Chemische Werke Ag | Process for agglomerating synthetic rubber dispersions |
| US3318831A (en) * | 1963-12-16 | 1967-05-09 | Copolymer Rubber & Chem Corp | Process for preparing high solids concentrated latex |
| US4385164A (en) * | 1976-03-10 | 1983-05-24 | The Goodyear Tire & Rubber Company | Block copolymer dispersion stabilizer and aqueous dispersion polymerization therewith |
| US4308912A (en) * | 1979-03-28 | 1982-01-05 | Knecht Bernath L | Heat transfer system |
| NO860171L (en) * | 1985-01-30 | 1986-07-31 | Japan Synthetic Rubber Co Ltd | PROCEDURE FOR MANUFACTURE OF LARGE POLYMER PARTICLES. |
| JP2508083B2 (en) * | 1987-05-19 | 1996-06-19 | 大日本インキ化学工業株式会社 | Method for producing emulsion polymer |
-
1989
- 1989-12-21 US US07/454,544 patent/US5294659A/en not_active Expired - Fee Related
-
1990
- 1990-11-22 CA CA002030615A patent/CA2030615A1/en not_active Abandoned
- 1990-11-27 ES ES90122618T patent/ES2075870T3/en not_active Expired - Lifetime
- 1990-11-27 EP EP90122618A patent/EP0433710B1/en not_active Expired - Lifetime
- 1990-11-27 DE DE69021179T patent/DE69021179T2/en not_active Expired - Fee Related
- 1990-11-30 JP JP33094590A patent/JP3162703B2/en not_active Expired - Fee Related
- 1990-12-19 AU AU68246/90A patent/AU647060B2/en not_active Ceased
- 1990-12-20 KR KR1019900021153A patent/KR100201674B1/en not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US330795A (en) * | 1885-11-17 | James macphail | ||
| FR1337809A (en) * | 1961-09-26 | 1963-09-20 | Us Rubber Co | Synthetic rubber latex of the butadiene polymer type |
| FR2235966A1 (en) * | 1973-07-06 | 1975-01-31 | Mitsubishi Rayon Co | Agglomerisation of synthetic rubber particles in latex - by addn of acrylate copolymer latex at controlled pH |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0433710A3 (en) | 1991-12-04 |
| KR910011924A (en) | 1991-08-07 |
| AU6824690A (en) | 1991-06-27 |
| EP0433710A2 (en) | 1991-06-26 |
| CA2030615A1 (en) | 1991-06-22 |
| ES2075870T3 (en) | 1995-10-16 |
| US5294659A (en) | 1994-03-15 |
| JP3162703B2 (en) | 2001-05-08 |
| EP0433710B1 (en) | 1995-07-26 |
| KR100201674B1 (en) | 1999-06-15 |
| DE69021179T2 (en) | 1996-03-14 |
| JPH03212401A (en) | 1991-09-18 |
| DE69021179D1 (en) | 1995-08-31 |
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